CN104513906A - Non-saponification extraction separation method of rare-earth element - Google Patents
Non-saponification extraction separation method of rare-earth element Download PDFInfo
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Abstract
The invention relates to a synergistic extraction separation method of a rare-earth element, in particular to a non-saponification extraction separation method of the rare-earth element. According to the invention, a non-saponification acid extraction agent (P204 or P507) and an alkaline extraction agent (N1923, N179, N116, DDA and DLA) are mixed according to a certain proportion to form a synergistic extraction agent, after the synergistic extraction agent and a diluent are mixed to react with a mineral acid, deionized water is used for washing the reacted product to be neutral, and the neutral reacted product is used for extraction separation of the rare-earth element. Saponification treatment is not needed to be performed on the extraction agent in the extraction process of the rare-earth element, so that the problems that ammonia nitrogen waste water and the like produced by the saponification treatment pollute environment and the like can be solved; in addition, the technological process is simple to operate, and the production cost is reduced to a certain extent.
Description
Technical field
The present invention relates to a kind of method of synergistic extraction separation of rare earth elements, particularly relate to a kind of method of non-saponifiable extraction separation of rare earth elements.
Background technology
15 kinds of elements of group of the lanthanides and yttrium, these 17 kinds of elements of scandium are referred to as rare earth element, and because rare earth element character is close, therefore separating-purifying acquisition Rare Earth Elements Determination is more difficult.Separating technology and the method for current industrial rare earth element are more, wherein solvent extration is because the product purity and yield with production is high, chemical reagent consumption is few, production environment good, production process is carried out continuously, easily is automated the advantages such as control, is Rare Earth Separation industrial application processing method very widely.
Mainly use acidic extractant, P204 and P507 in the solvent extraction and separation method of China's rare earth element, this kind of extractants shows as slightly acidic, usually exists with dimeric form in kerosene polar solvent,
In formula: M
n+represent rare earth element;
(HA) be acidic extractant monomer.
Can find out that from formula (1) reaction process of P204 or P507 and rare earth element is base exchange process, hydrogen ion and rare earth ion that extraction agent during extractive reaction occurs exchange, and the hydrogen ion concentration therefore in the aqueous solution increases.
Can show that the relation of partition ratio and acidity is such as formula (2) through the derivation of equation
As can be seen from formula (2), partition ratio lgD and pH is directly proportional, and namely the partition ratio of the larger rare earth element of pH value in organic phase is larger.And along with hydrogen ion concentration in solution often increases by 10 units (namely pH value increases a unit), then partition ratio will reduce 10
3individual unit.The impact of the hydrogen ion discharged in the process of therefore extracting and separating rear earth element on extraction is very large.
The rising of aqueous solution hydrogen ion concentration in extraction process, usually before extractive reaction occurs, adopt the alkaline liquid such as sodium hydroxide or ammoniacal liquor to carry out saponification process to acidic extractant P204 or P507 in current industry, its main purpose is by the reaction of acid with alkali, hydrogen ion in acidic extractant hydroxyl is replaced by alkaline kation, and these positively charged ions are discharged in the aqueous solution in extraction process, the hydrogen ion concentration thus in solution can not increase.Adopt NaOH as the cost of saponifying agent relatively high and in the waste water of saponification salts contg exceed standard, saline Land degree can be made to increase the weight of if be discharged in soil.Adopt strong aqua processing cost relatively low, but the ammonia-nitrogen content in waste water can be caused to increase, after discharge, meeting severe contamination water body, makes treatment cost greatly increase.
In order to solve the problem that this saponification process brings.The extensive work done both at home and abroad is nothing but adopt the means of non-saponified to replace saponification process, thus replaces the use of saponifiable extraction system.Patent CN1824814 has invented the acid of a kind of employing acidic organo phosphorus or organophosphate kind of extractants as P204, P507, C272, mixed extractant extracting and separating rear earth element in rare earth chloride or rare earth nitrate solution of a kind of or 2-3 kind preparation wherein such as P229, when using the method extracting and separating rear earth, organic extractant does not need saponification, waste water is not produced in extraction process, the pollution of ammonia nitrogen waste water to water resources can be eliminated, although the method replaces the method for saponification process with composite extractant, but extraction agent is weakly acidic organic phosphoric acid or organophosphorus compounds, the method improves the ability of extracting and separating rear earth by the synergistic effect of composite extractant, and aqueous phase acidity can not be regulated, so composite extractant is still larger on the impact of solution acidity in the process of carrying out extracting and separating rear earth element.Patent CN101709392A has invented a kind of method that method by dilution aqueous phase reduces hydrionic concentration in the aqueous solution, this method avoid the generation of ammonia nitrogen waste water, also reduce production cost simultaneously, but the method also makes the concentration of rare earth feed liquid reduce while reduction hydrogen ion concentration, and therefore production efficiency also reduces greatly.The people such as Xiao Yanfei (XIAO Yanfei, LONG Zhiqi, HUANG Xiaowei. Study on non-saponification extraction process for rare earth separation [J]. Journal of Rare Earths, 2013, 31:512-516.) adopt additional magnesium oxide to regulate the hydrogen ion concentration of aqueous phase, thus reduce hydrogen ion to the impact of extraction process, although the method can effectively control aqueous phase hydrogen ion concentration, but additional magnesium oxide easily produces the effect that third phase has a strong impact on rare earth element extracting and separating in the process of extracting and separating rear earth element.
Summary of the invention
The object of the present invention is to provide and a kind ofly the aqueous solution rare earth elements containing two or more rare earth element can be made to be separated, time simultaneously in order to avoid using acidic extractant system to carry out rare earth element extracting and separating, in acidic extractant, hydrogen ion and rare earth ion generation replacement(metathesis)reaction make hydrogen ion concentration in aqueous phase raise, cause affecting the problem that extraction agent reduces greatly to rare earth element extracting and separating ability, and the saponification pre-treatment replacing alkali by adopting synergic reagent to carry out rare earth element extracting and separating, avoid the method for the non-saponifiable extraction separation of rare earth elements of the environmental problem that the use due to saponifying agent brings.
technical solution
The present invention forms synergic reagent after adopting the acidic extractant of non-saponified to mix by a certain percentage with basic extractant, after the organic phase of this synergic reagent and mixing diluents and mineral acid react, be washed till neutral liquid with deionized water, through with acid-respons, wash after organic phase and rare earth feed liquid to react extracting and separating rear earth element.
In described synergic reagent, the acidic extractant of non-saponified is P204, P507 or naphthenic acid.
Described synergic reagent neutral and alkali extraction agent refers to N1923, N179, N116, DDA or DLA extraction agent.
In described synergic reagent, the acidic extractant of non-saponified mixes by certain volume with the basic extractant after mineral acid treatment, and wherein acidic extractant accounts for 50%-95%, and basic extractant accounts for 50%-5%.
Described thinner is sulfonated kerosene, tetracol phenixin, hexanaphthene or heptane.
Described synergic reagent is respectively 2:1,3:2,1:1,1:2,1:3,1:4 or 1:5 ratio with thinner according to volume and mixes.
Organic phase after described synergic reagent and mixing diluents and 3mol/L mineral acid react according to volume ratio 4:1-1:1, wash the spent acid in organic phase after reaction with water.
Described mineral acid refers to the solution of one or more mixing in hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid;
Described rare earth feed liquid is the aqueous chloride solution containing two or more rare earth element, and the content of this aqueous chloride solution rare earth elements is with rare earth oxide summation meter mass concentration for REO=10 ~ 300 grams per liter, and the pH value of earth solution is 0-3.
The present invention adopts the acidic extractant of non-saponified and basic extractant to mix the novel synergic reagent of rear formation by a certain percentage, after the organic phase that this extraction agent and mixing diluents are formed and mineral acid react, repeatedly wash to neutrality with deionized water, through with acid-respons, wash after organic phase be used for extracting and separating rear earth concentration be that 10-300g/L(is by REO), pH value is the rare earth mixed liquor between 0-4.5.
The present invention is made up of 3 operations:
Operation 1: the preparation of synergic reagent
Non-saponified acidic extractant extracting and separating rear earth element technique, the acidic extractant adopting non-saponified process to account for volume fraction 5%-50% is made into organic phase with the basic extractant and sulfonated kerosene (accounting for volume fraction 50%) accounting for volume fraction 5%-50% by certain proportioning, the mineral acid of this organic phase and 3mol/L, according to after volume ratio 1:1 hybrid reaction, repeatedly washs to neutrality with deionized water.
Operation 2: the preparation of rare earth feed liquid
Rare earth feed liquid be through that the rare-earth mineral of acid dissolve obtains earth solution wherein rare earth concentration be that 10-300g/L(is by REO), pH value controls between 0-4.5.Dissolving acid used is hydrochloric acid, nitric acid, sulfuric acid, or their mixing acid.
Operation 3: organic phase back extraction regenerates
Adopt the hydrochloric acid of 0.5-6.0mol/L, sulfuric acid, nitric acid, or their mixing acid carrys out back extraction load organic phases, acid higher strip liquor also can be adopted to carry out back extraction load organic phases.Organic phase after back extraction have certain acidity may be used for back extraction load organic phases also may be used for dissolve leach rare-earth mineral.
Organic extractant phase neutral water after back extraction repeatedly washs according to a certain percentage, and the back extraction acid solution of gained can be used for other operation through enrichment method.
feature of the present invention
The present invention adopts the acidic extractant of non-saponified and basic extractant to mix the novel synergic reagent of rear formation by a certain percentage, after this extraction agent and mixing diluents and mineral acid react, be washed till neutral liquid with deionized water, through with acid-respons, wash after organic phase be used for the extracting and separating of rare earth element.Because extraction agent does not need saponification and synergic reagent can absorb certain hydrogen ion in extraction process, thus on source, solving extraction agent release hydrogen ions to extracting the impact caused, the method can solve the problem of environmental pollution that saponification treatment process causes.
Embodiment
Below with the example implemented, the present invention is further illustrated.Because the limited protection scope of the present invention of example does not limit by example, protection scope of the present invention is determined by claim content.
Embodiment 1
Raw material take mixed rare earth carbonate as raw material, rare-earth chloride solution is obtained with the dissolving with hydrochloric acid of 3mol/L, the total concn REO=250g/L of rare-earth chloride solution rare earth elements, partition of rare earth element is wherein with oxide basis, and the percentage ratio of each rare earth element quality and total rare earth oxide compound REO mass ratio is: La
2o
3/ REO=26.75%; CeO
2/ REO=50.00%; Pr
6o
11=5.50%/REO; Nd
2o
3/ REO=15.50%; Middle heavy rare earths (with oxide basis)/REO=2.25%., the pH regulating rare earth aqueous solution is 1.0-1.4.
Organic phase is after unsaponified P507 and N1923 is mixed into synergic reagent and sulfonated kerosene is made into organic solution according to certain volume ratio, wherein in synergic reagent, P507 volume fraction is 50%, N1923 volume fraction is 50%, synergic reagent and kerosene are that 1:1 is mixed into organic phase according to volume ratio, after 2:1 reacts by volume with 3mol/L sulfuric acid, being washed to neutrality becomes extracted organic phase.Then carry out Nd/Sm grouping with rare-earth chlorination solution fractionation extraction mode, adopt 16 grades of extractions, 12 grades of washings, 8 grades of back extractions, compare (unit L/min): organic phase: earth solution: washing lotion=2.6:1:0.51; Washing section adopts the salt acid elution of 3N; With the hydrochloric acid back extraction of 6N.Last extracting and separating obtains containing middle heavy rare earths with the solution of oxide basis (hereafter identical) about 220g/L, and this solution is for the production of middle heavy rare-earth oxide product.
Obtain raffinate through above-mentioned Nd/Sm grouping separation, carry out Ce/Pr separation in fractionation extraction mode.Adopt 56 grades of extractions, 53 grades of washings, 8 grades of back extractions, compare (unit L/min): organic phase: earth solution: washing lotion=8.2:1:0.84; Washing section adopts the salt acid elution of 3N; Strip with the hydrochloric acid of 6N.Last extracting and separating obtains the solution being about 200g/L containing praseodymium neodymium oxides, and this solution can be used for producing praseodymium neodymium oxides product.
Be separated the raffinate containing lanthanum Ce elements obtained through Ce/Pr, carry out La/Ce separation in fractionation extraction mode.Compare (unit L/min): organic phase: earth solution: washing lotion=9.1:1:0.4; Through extracting 29 grades, washing 40 grades, being separated in the fractionation extraction groove of 8 grades of stripping; The salt acid elution of organic phase 3N, the hydrochloric acid of 6N is stripped, and obtains containing CeO
2the solution of=220g/L, this solution is for the production of cerium oxide product.
Embodiment 2
Raw material is mixed rare-earth oxide, contains the total concn REO=35g/L of rare earth element in mixed rare-earth oxide with hydrochloric acid melt into, and partition of rare earth element is wherein in the same manner as in Example 1, and the pH regulating rare earth aqueous solution is 0-0.8.
Organic phase is after unsaponified P204 and N179 is mixed into synergic reagent and tetracol phenixin is made into organic solution according to certain volume ratio, wherein in synergic reagent, P204 volume fraction is 65%, N179 volume fraction is 35%, synergic reagent and tetracol phenixin are that 2:1 is mixed into organic phase according to volume ratio, after 1:1 reacts by volume with 3mol/L hydrochloric acid, being washed to neutrality becomes extracted organic phase.18 stage countercurrent modes are adopted to extract all rare earth elements, compare (unit L/min): organic phase: earth solution: washing lotion=0.9:1:0.3, the organic phase 6N hydrochloric acid soln of extraction supported rare earth element to be stripped rare earth element in 8 stage countercurrent modes, and organic phase returns counter-current extraction rare earth operation and recycles.The mixed rare earth solution that extracting and separating obtains can be prepared mixed rare-earth oxide further or be separated single rare earth product according to the method for embodiment 1.The yield of whole process rare earth element is greater than 95%.
Embodiment 3
Raw material is mixed chlorinated rare earth solution, total concn REO=200g/L containing rare earth element in mixed chlorinated rare earth solution, partition of rare earth element wherein with the percentage ratio of each rare earth element quality of oxide basis and total rare earth oxide compound REO mass ratio is: La
2o
3/ REO=51.0%; CeO
2/ REO=17.0%; Pr
6o
11=10.0%/REO; Nd
2o
3/ REO=20.0%; Middle heavy rare earths (with oxide basis)/REO=2.0%., the pH regulating rare earth aqueous solution is 3-4.
Organic phase is after unsaponified naphthenic acid is mixed into synergic reagent with N116 and hexanaphthene is made into organic solution according to certain volume ratio, wherein in synergic reagent, naphthenic acid volume fraction is 70%, N116 volume fraction is 30%, synergic reagent and kerosene are that 2:3 is mixed into organic phase according to volume ratio, after 3:1 reacts by volume with 3mol/L nitric acid, being washed to neutrality becomes extracted organic phase.Then carry out Nd/Sm grouping with rare-earth chlorination solution fractionation extraction mode, extract 17 grades, wash 21 grades, carry out in the fractionation extraction groove of 8 grades of stripping; Stream is than being: organic phase: earth solution: washing lotion=2.5:1:0.4; Nd, Pr and Ce, La are separated in extraction 52 grades, wash 45 grades, carry out in the fractionation extraction groove of 8 grades of stripping, and stream is than being: organic phase: earth solution: washing lotion=7.8:1:0.95; Ce and La is separated and is separated in extraction 27 grades, washs 24 grades, carries out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=7.5:1:0.6.Other processes are identical with embodiment 1.
The purity of the earth oxide product obtained is respectively Pr
6o
11+ Nd
2o
3/ REO>=99.9%; CeO
2/ REO>=99%; La
2o
3/ REO>=99%; Sm Eu Gd concentrate (Eu
2o
3/ REO>=8%).Whole process, the yield of rare earth element is greater than 95%, and purity is greater than more than 99%.
Embodiment 4
Raw material is mixed chlorinated rare earth solution, and the total concn REO=50g/L partition of rare earth element wherein containing rare earth element in mixed chlorinated rare earth solution with the percentage ratio of each rare earth element quality of oxide basis and total rare earth oxide compound REO mass ratio is: La
2o
3/ REO=31.0%; CeO
2/ REO=37.0%; Pr
6o
11/ REO=7.5.0%; Nd
2o
3/ REO=22%; Middle heavy rare earths (with oxide basis)/REO=2.5%, the pH regulating rare earth aqueous solution is 2-3.
Organic phase is after unsaponified P507 and N1923 is mixed into synergic reagent and thinner heptane is made into organic solution according to certain volume ratio, wherein in synergic reagent, P507 volume fraction is 95%, N1923 volume fraction is 5%, synergic reagent and kerosene are that 1:3 is mixed into organic phase according to volume ratio, after the 4:1 reaction by volume of 3mol/L hydrofluoric acid, being washed to neutrality becomes extracted organic phase.Then carry out Nd/Sm grouping with rare-earth chlorination solution fractionation extraction mode, extract 17 grades, wash 21 grades, carry out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=2.5:1:0.4; Nd, Pr and Ce, La are separated in extraction 52 grades, wash 45 grades, carry out in the fractionation extraction groove of 8 grades of stripping, and stream is than being: organic phase: earth solution: washing lotion=7.8:1:0.95; Ce and La is separated and is separated in extraction 27 grades, washs 24 grades, carries out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=7.5:1:0.6.Other processes are identical with embodiment 1.
The purity of the earth oxide product obtained is respectively Pr
6o
11+ Nd
2o
3/ REO>=99.9%; CeO
2/ REO>=99%; La
2o
3/ REO>=99%; Sm Eu Gd concentrate (Eu
2o
3/ REO>=8%).Whole process, the yield of rare earth element is greater than 95%, and purity is greater than more than 99%.
Embodiment 5
Raw material is mixed chlorinated rare earth solution, and the total concn REO=125g/L partition of rare earth element wherein containing rare earth element in mixed chlorinated rare earth solution with the percentage ratio of each rare earth element quality of oxide basis and total rare earth oxide compound REO mass ratio is: La
2o
3/ REO=42.0%; CeO
2/ REO=21.0%; Pr
6o
11=22%/REO; Nd
2o
3/ REO=12.25%; Middle heavy rare earths (with oxide basis)/REO=2.75%., the pH regulating rare earth aqueous solution is 2-2.5.
Organic phase is after unsaponified P507 and DDA is mixed into synergic reagent and sulfonated kerosene is made into organic solution according to certain volume ratio, wherein in synergic reagent, P507 volume fraction is 85%, N1923 volume fraction is 15%, synergic reagent and kerosene are that 1:4 is mixed into organic phase according to volume ratio, after the 2:1 reaction by volume of 3mol/L hydrochloric acid, being washed to neutrality becomes extracted organic phase.Then carry out Nd/Sm grouping with rare-earth chlorination solution fractionation extraction mode, extract 17 grades, wash 21 grades, carry out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=2.5:1:0.4; Nd, Pr and Ce, La are separated in extraction 52 grades, wash 45 grades, carry out in the fractionation extraction groove of 8 grades of stripping, stream than being, organic phase: earth solution: washing lotion=7.8:1:0.95; Ce and La is separated and is separated in extraction 27 grades, washs 24 grades, carries out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=7.5:1:0.6.Other processes are identical with embodiment 1.
The purity of the earth oxide product obtained is respectively Pr
6o
11+ Nd
2o
3/ REO>=99.9%; CeO
2/ REO>=99%; La
2o
3/ REO>=99%; Sm Eu Gd concentrate (Eu
2o
3/ REO>=8%).Whole process, the yield of rare earth element is greater than 95%, and purity is greater than more than 99%.
Embodiment 6
Raw material is mixed chlorinated rare earth solution, and the partition of rare earth element wherein of the total concn REO=170g/L containing rare earth element with the percentage ratio of each rare earth element quality of oxide basis and total rare earth oxide compound REO mass ratio is: La
2o
3/ REO=62.0%; CeO
2/ REO=22.5%; Pr
6o
11=7.25%/REO; Nd
2o
3/ REO=6.2%; Middle heavy rare earths (with oxide basis)/REO=2.05%., the pH regulating rare earth aqueous solution is 1.5-2.5.
Organic phase is after unsaponified P204 and DLA is mixed into synergic reagent and hexanaphthene is made into organic solution according to certain volume ratio, wherein in synergic reagent, P204 volume fraction is 60%, DLA volume fraction is 40%, synergic reagent and kerosene are that 1:1 is mixed into organic phase according to volume ratio, after the 3:1 reaction by volume of 3mol/L sulfuric acid, being washed to neutrality becomes extracted organic phase.Then carry out Nd/Sm grouping with rare-earth chlorination solution fractionation extraction mode, extract 17 grades, wash 21 grades, carry out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=2.5:1:0.4; Nd, Pr and Ce, La are separated in extraction 52 grades, wash 45 grades, carry out in the fractionation extraction groove of 8 grades of stripping, stream than being, organic phase: earth solution: washing lotion=7.8:1:0.95; Ce and La is separated and is separated in extraction 27 grades, washs 24 grades, carries out in the fractionation extraction groove of 8 grades of stripping; Flow than being, organic phase: earth solution: washing lotion=7.5:1:0.6.Other processes are identical with embodiment 1.
The purity of the earth oxide product obtained is respectively Pr
6o
11+ Nd
2o
3/ REO>=99.9%; CeO
2/ REO>=99%; La
2o
3/ REO>=99%; Sm Eu Gd concentrate (Eu
2o
3/ REO>=8%).Whole process, the yield of rare earth element is greater than 95%, and purity is greater than more than 99%.
Claims (8)
1. the method for non-saponifiable extraction separation of rare earth elements, it is characterized in that: after adopting the acidic extractant of non-saponified to mix by a certain percentage with basic extractant, form synergic reagent, after the organic phase of this synergic reagent and mixing diluents and mineral acid react, be washed till neutral liquid with deionized water, through with acid-respons, wash after organic phase and rare earth feed liquid to react extracting and separating rear earth element.
2. non-saponifiable extraction rare-earth separating method according to claim 1, is characterized in that: in described synergic reagent, the acidic extractant of non-saponified is P204, P507 or naphthenic acid.
3. non-saponifiable extraction rare-earth separating method according to claim 1, is characterized in that: described synergic reagent neutral and alkali extraction agent refers to N1923, N179, N116, DDA or DLA extraction agent.
4. the non-saponifiable extraction rare-earth separating method according to claim 1,2 or 3, it is characterized in that: in described synergic reagent, the acidic extractant of non-saponified mixes by certain volume with the basic extractant after mineral acid treatment, wherein acidic extractant accounts for 50%-95%, and basic extractant accounts for 50%-5%.
5. a kind of non-saponifiable extraction rare-earth separating method according to claim 1, is characterized in that: described thinner is sulfonated kerosene, tetracol phenixin, hexanaphthene or heptane.
6. non-saponifiable extraction rare-earth separating method according to claim 1, is characterized in that: described synergic reagent is respectively 2:1,3:2,1:1,1:2,1:3,1:4 or 1:5 ratio with thinner according to volume and mixes.
7. a kind of non-saponifiable extraction rare-earth separating method according to claim 1 or 6, it is characterized in that: the organic phase after described synergic reagent and mixing diluents and 3mol/L mineral acid react according to volume ratio 4:1-1:1, wash the spent acid in organic phase after reaction with water.
8. the method for the non-saponifiable extraction separation of rare earth elements according to claim 1 or 7, is characterized in that: described mineral acid refers to the solution of one or more mixing in hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid;
The method of non-saponifiable extraction separation of rare earth elements according to claim 1, it is characterized in that: described rare earth feed liquid is the aqueous chloride solution containing two or more rare earth element, the content of this aqueous chloride solution rare earth elements is with rare earth oxide summation meter mass concentration for REO=10 ~ 300 grams per liter, and the pH value of earth solution is 0-3.
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| CN107604162A (en) * | 2015-12-24 | 2018-01-19 | 广西师范大学 | A kind of mixed extractant for separating yttrium |
| CN107699715A (en) * | 2016-08-08 | 2018-02-16 | 有研稀土新材料股份有限公司 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| CN107699715B (en) * | 2016-08-08 | 2019-10-01 | 有研稀土新材料股份有限公司 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| CN110331303A (en) * | 2019-08-13 | 2019-10-15 | 包头稀土研究院 | The method of heavy rare earth chloride solution in continuous extraction separation |
| CN110331303B (en) * | 2019-08-13 | 2022-03-18 | 包头稀土研究院 | Method for continuously extracting and separating medium-heavy rare earth chloride solution |
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